Pycnoporus sanguineus (Ps) 1 and Candida tropicalis (Ct) can selectively degrade the lignin and hemicellulose in lignocellulosic cells respectively; Ps-Ct mixed fermentation may improve the multiphase reaction performance of lignin in the cell walls. Alkaline nitrobenzene oxidation, ozonation and infrared spectroscopy, which are the in-situ analytical techniques of lignin in the cells, were used to characterize the delignification kinetics, the reactions of the non-condensed, β-O-4 structures and their stereochemistry of lignin in wheat straw in Ps and Ps-Ct fermentations. Results indicated that the biodelignification processes in Ps and Ps-Ct fermentations of wheat straw, being divided into a fast phase and a following slow phase, had the characteristics of a pseudo-first-order reaction in both the phases. The lignin reaction pathways in Ps and Ps-Ct mainly included the cleavage of ring, C α -C β , β-O-4, and the cleavage and polymerization of 5-5´. Compared with Ps fermentation, Ps-Ct fermentation enhanced the 1 ABBREVIATIONS Ps, Pycnoporus sanguineus; Ct, Candida tropicalis 2 biodegradation of condensed, β-O-4 structures and threo β-O-4 structures in the lignin in the fast phase. A proposal scheme of biodelignification by Ps and Ps-Ct is outlined for the first time.These results will be helpful for the understanding and application of lignocellulosic biomass by mixed fermentations.